CN107389779A - A kind of rapid analysis method of chemical constitution - Google Patents
A kind of rapid analysis method of chemical constitution Download PDFInfo
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Abstract
This application provides a kind of rapid analysis method of chemical constitution, including：By gas phase or liquid phase mixture direct injected in gas phase or liquid phase mass spectrograph, the first mass spectrometric of each composition in mixture is obtained by soft ionization method afterwards, change parameter again and obtain two-dimentional mass spectrum to increase one or more disturbances, two-dimentional mass spectrum is parsed by dynamics entropy minimum method afterwards, finds each independent ion and corresponding dynamic process；Then each separate ionization formula is extrapolated using the high-resolution mass-to-charge ratio data of independent ion, or compared with existing independent ion and Chemical kintics database and determine the structural formula of each independent ion, and then determine the chemical formula or chemical constitution of each composition in mixture.The application method is minimum for primary sample demand, and sample does not need pre-treatment, and easy to operate, analysis result is accurate, is advantageous to use the structure of the unknown material and known substance in the quick analysis of mixtures of gas phase and liquid phase mass spectrograph.
Description
Technical field
The application is specifically related to a kind of rapid analysis method of chemical constitution, for quickly find mixture in it is various not
Know the chemical formula or chemical constitution with known substance composition, belong to chemical analysis field.
Background technology
It was found that the structure of the non-principal component in mixture is a very attractive field, have extensively using value.Example
Such as, in various traditional Chinese medicine ingredients, it is not also known to have many non-principal components, and their medical value and commercial value is all urgently opened
Hair.However, the non-principal component in analysis of mixtures is also very challenging.For example, nuclear magnetic resonance spectroscopy (NMR
Spectroscopy it is) a kind of technological means common in chemical analysis field, unknown material is analyzed with nuclear magnetic resonance spectroscopy
Structure, very can accurately obtain its structure.But it is purer to analyze structure of matter needs with nuclear magnetic resonance spectroscopy
Sample.This method is frequently necessary to tens kilograms of Chinese medicine, by separating for several times and purification, takes a significant amount of time, money and manpower,
The pure component of Gamma Magnitude is finally obtained, just can analyze its chemical constitution using nuclear magnetic resonance spectroscopy.So analyzed with this
The various composition that method is come in analysis of mixtures extremely wastes time and energy, it is necessary to very professional personnel, and in many Chinese medicines
Micro constitutent is lost or destroyed in pretreatment process, thus can not also be found.
Mass spectrum (Mass Spectroscopy, MS) analytic approach is another particularly significant and common in chemical analysis field
Technological means.Mass spectrum be one kind by ionizing material, it is then each to analyze material according to the mass-to-charge ratio (m/z) of ionization material
The chemical analysis means of kind characteristic (such as organic components structure, isotopic composition etc.), are widely used in every field.Mass spectrum
It is a kind of very conventional organic principle Qualitative.Mass spectrograph makes the powered mode of material include soft ionization (soft
Ionization (hard ionization) mode) and is firmly ionized.Soft ionization mode is a kind of relatively low ionization side of relative energy
Formula, so in ionization process, less fragment can be produced, retain molecular ion (molecular ion) sometimes.Common
Soft ionization mode includes chemi-ionization (CI, Chemical Ionization), electro-spray ionization (ESI, Electrospray
Ionization), Atmospheric Pressure Chemical ionization (APCI, Atmospheric-Pressure Chemical Ionization)
Deng.Hard ionization mode then gives sample large energy, causes chemical bond rupture or molecular rearrangement using high-velocity electrons impact sample, from
And produce a variety of fragment ions.Common hard ionization mode includes electron bombardment (EI, Electron Ionization) etc..
Because mass spectrum is a kind of detector, it is combined so generally requiring with other Chemical Decomposition analysis means, to reach more
Add accurately separation and analysis purpose.For example, mass spectrum can combine gas-chromatography or liquid chromatography technology (application of gas chromatorgraphy/mass technology),
Form gas chromatography mass spectrometer (abbreviation gaseous mass spectrum) or liquid chromatography mass instrument (abbreviation liquid chromatography mass spectrometric).Chromatogram utilizes not jljl
The absorption affinity difference of confrontation adsorbent separates various materials so that mixture is separated before mass spectrum is entered, so as to mass spectrograph
More accurately analyze various composition.Under normal circumstances, single mass spectrograph is not used in analysis of mixtures.
For other analytical technologies, with application of gas chromatorgraphy/mass technology come the known substance constituent structure in analysis of mixtures,
The pre-treatments such as the purification that is excessively taken time and effort to known substance are not required to, directly can be analyzed using mixture, convenient letter
It is clean.Individually with being extremely difficult with the unknown material in chromatographic technique analysis of mixtures, because even chromatographic isolation goes out unknown material,
, cannot qualitative unknown material because no database compares.In general, unknown material structure is analyzed, it is necessary to utilize nuclear magnetic resonance
Or mass spectrum.However, it is still old many difficult come the unknown material in analysis of mixtures using mass spectrum, such as：
1) under normal circumstances, using mass-spectrometric technique come the unknown material in analysis of mixtures, it is necessary to utilize MSnTechnology, that is, go here and there
Join mass-spectrometric technique, and tandem mass spectrum technology can bring substantial amounts of information, the mass ions much obtained in different collision energy sections
Fragment mixes, and extremely disturbs mass spectrographic parsing, so as to add the difficulty to interpretation of mass spectra；In addition, with secondary matter
The increase of number is composed, Information in Mass Spectra is more and more, and complexity is also bigger, and it is more and more difficult to analyze its structure.
2) compared to liquid phase ingredient, the structural analysis of gas phase composition is extremely difficult in fact.For analyzing and identifying gas phase
Non- principal component in composition, nowadays also without effective technology, it is main reason is that the non-principal component of gas phase is very difficult to richness
Collection and purification.And because gas phase composition is nonpolar by force, molecular weight is small, be difficult to be coupled with electric charge in liquid chromatography mass spectrometric, therefore it is difficult
To be detected with liquid phase mass spectrograph, so qualitative extremely difficult.
3) due to the complexity of mass-spectrometric technique, parsing mass spectrographic to unknown material is relatively difficult, it usually needs Duo Zhongzhuan
Industry knowledge and experience, so needing senior professional to carry out, cost is high, and professional's number is seldom, therefore limits
Mass-spectrometric technique is in unknown material composition and the application of structural analysis.
4) requirement of the existing method due to its complexity and to personnel is high, can not be analyzed automatically using instrument.
The content of the invention
The main purpose of the application is to provide a kind of rapid analysis method of chemical constitution, this method binding kineticses entropy
Minimum method and mass spectral analysis, it can quick and precisely, automatically find various unknown in gas phase and liquid phase mixture and principal component
Chemical formula or chemical constitution, with overcome the deficiencies in the prior art.
To achieve these goals, the technical scheme that the application uses includes：
The embodiment of the present application provides a kind of rapid analysis method of chemical constitution, and it includes：
(1) by gas phase or liquid phase mixture sample introduction in gas phase or liquid phase mass spectrograph；
(2) the one of the mixture is obtained by analyzing the mixture in a manner of soft ionization by the mass spectrograph
Level mass spectrogram；
(3) in multiple quasi-molecular ions that the first mass spectrometric figure obtained from step (2) includes, a unknown or known molecular is chosen
First mass spectrometric peak, and choose one or more parameters when the mass spectrograph is detected as disturbed conditions, and set institute
One group of difference numerical value under disturbed conditions is stated, is further analyzed under the different value conditions of the disturbed conditions, is obtained
Multiple second order mses figures corresponding with the first mass spectrometric peak, the multiple second order mses that will be obtained afterwards under different disturbed conditions
Figure synthesis, obtains two-dimentional mass spectrometric data collection；
(4) the two-dimentional mass spectrometric data collection obtained to step (3) is calculated by dynamics entropy min algorithm, described in acquisition
Each independent ion at first mass spectrometric peak and corresponding dynamic process；
(5) each independent ion obtained for step (4), using the testing result of high-resolution mass spectrometer, extrapolate each
The chemical formula of individual independent ion, or, each independent ion and corresponding dynamic process that step (4) is obtained with it is known solely
The database of vertical ion and dynamic process compares, and determines the structural formula of each independent ion；
(6) chemical formula or structural formula of each independent ion obtained according to step (5), is inferred to the first mass spectrometric peak
Corresponding chemical formula or structural formula.
Further, step (1) includes：Gas phase or liquid phase mixture are not done into any separation, and direct injected is in gas phase
Or liquid phase mass spectrograph.
Further, in step 1), the gas phase or liquid phase mass spectrograph have more than acquisition two level mass spectrographic function, and energy
In the mass spectrum shattering process of different stage, there is provided various disturbances.
Further, in step 1), the gas phase or liquid phase mass spectrograph include quadrupole rod time of-flight mass spectrometer, San Chongsi
Level bar mass spectrograph, ion trap mass spectrometer, ion-trap time-of-flight mass spectrometer, time-of-flight mass spectrometry instrument or electrostatic field orbit trap
Combined type mass spectrograph etc., but not limited to this.
Further, using soft ionization mode, to make, various unknown in mixture and principal component is powered in step 2)
Further, the soft ionization mode in step 2) includes chemi-ionization method, electro-spray ionization method, atmospheric pressure
Power chemi-ionization method or substance assistant laser desorpted ionized method etc., but not limited to this.
Further, the disturbed conditions used in step 3) include electric-field intensity, magnetic field intensity, radiation intensity, vacuum,
Any one or a few combination in the size and species of colliding molecule, the wavelength of excitation source or intensity, but not limited to this.
Further, step 5) includes：Using the high-resolution mass-to-charge ratio data of each independent ion, reckoning obtain each independence from
The chemical formula of son.
Further, step 5) includes：Analyzed, obtained by carrying out dynamics entropy minimum method to different principal components
The independent ion and corresponding dynamic process of these known or non-principal components, and establish the independent ion based on these compositions
With the database of dynamic process.
Further, step 6) includes：The chemical formula of each independent ion obtained using step (5) and step (3) institute
The molecular information obtained, it is inferred to the chemical formula of corresponding unknown material or known substance.
Further, step 6) includes：The structural formula of each independent ion obtained using step (5) and step (3) institute
The molecular information obtained, it is inferred to the structural formula of corresponding unknown material or known substance.
Than prior art, the application at least has the following advantages that：
1) using unknown and principal component chemical formula or chemical constitution in the present processes detection mixture, only need several
The sample of individual milligram, required sample are few.
2) using the present processes can Direct Analysis mixture, while each composition in analysis of mixtures sample and
A large amount of manpower and materials need not be spent to carry out a large amount of pre-treatments and each composition of separating-purifying.
3) each composition can be repeatedly smashed using the present processes, so as to obtain smaller structure, reduces smaller structure
Molecular structure after, to extrapolate the molecular structure of original matter.
4) the present processes are utilized, for same sample, only need to repeat abovementioned steps 3) to step 6), it is possible to it is accurate
The chemical formula or chemical constitution of each composition in analysis of mixtures.
5) when using the present processes analysis gas phase and liquid phase material, computerized algorithm can be added, it is very quickly sharp
The high-resolution fragment peak obtained with second order mses, according to it in the position of spectrogram and IP, quickly mark each broken
(because the molecular weight of composition in gas phase sample is small, fragment molecular weight is smaller, it is possible to very easily root for the molecular formula at piece peak
According to high-resolution fragment peak, the combination of the elements such as its C, H, O, N, S is obtained, so as to quickly know its structure).When having obtained fragment
After the molecular structure at peak, the molecular formula of parent peak (main peak do not smashed) is just easy to reduce, so as to obtain its molecular structure letter
Breath, find the chemical constitution of unknown material or known substance in mixture.
6) the present processes are utilized, the analysis for non-principal component in gas phase and liquid phase mixture, are not required to extremely have experience
Professional also can efficiently analyze the chemical formula or structural formula of non-principal component therein, save cost, it is time saving and energy saving.
Brief description of the drawings
It is right with reference to the accompanying drawings and detailed description in order to illustrate more clearly of the application architectural feature and technical essential
The application is described in detail.
Fig. 1 is a kind of schematic diagram of the rapid analysis method of chemical constitution in the embodiment of the application one.
Fig. 2 is that unknown material molecule dissociates obtained two-dimentional mass spectrogram group under different collision energies in the embodiment of the present invention 2
The two-dimentional mass spectrometric data collection obtained altogether.
Fig. 3 is the dynamic process that unknown material molecule is broken in the embodiment of the present invention 2.
Fig. 4 A- Fig. 4 E are the mass spectrograms of the broken caused independent ion A-E of unknown material molecule in the embodiment of the present invention 2.
Fig. 5 is that folate molecule dissociates obtained two-dimentional mass spectrogram under different collision gas pressure in the embodiment of the present invention 3
Combine obtained two-dimentional mass spectrometric data collection.
Fig. 6 is dynamic process of the folic acid under gas with various impact pressure.
Fig. 7 is independent ion A, B, C mass spectrogram caused by folic acid crushes under gas with various impact pressure.
Embodiment
As it was previously stated, in view of the deficiencies in the prior art, inventor are able to propose this through studying for a long period of time and largely putting into practice
The rapid analysis method of the chemical constitution of application, it, can be fast by binding kineticses entropy minimum method and mass spectrometric analysis method
Speed is accurate, automatically finds and analyzes various unknown in gas phase and liquid phase mixture and principal component chemical formula or chemical constitution,
The structural analysis being particularly suitable for use in the non-principal component in gas phase mixture, and then solve the puzzlement unknown constituent analysis of gas phase
Problem so that based on a small amount of gas phase composition, just can quickly analyze the structural information of non-principal component therein, and be mixed for liquid phase
The analysis of non-principal component in compound, also greatly reduce the complexity of multi-stage mses data message, it is not necessary to professional personage, just
The chemical formula or structural formula of the analysis non-principal component therein of energy efficiently and accurately.
Generally, this application provides unknown and known Components Chemical formula in combination algorithm and mass spectral analysis mixture or
The method of chemical constitution, preferably make the various composition in mixture powered by soft ionization mode first, while retain original point
Minor structure, then utilize MS1The molecular weight information of various composition is obtained, changes a certain parameter afterwards and is disturbed to increase one or more
It is dynamic to obtain two-dimentional mass spectrum, then two-dimentional mass spectrum is parsed by dynamics entropy minimum method, finds independent ion and power
Process, while the molecular formula or structural formula of independent ion are obtained according to certain rule, so as to be inferred to the molecule of initial molecule
Formula or structural formula.
Further, a kind of rapid analysis method for chemical constitution that the embodiment of the present application provides includes：By gas phase and liquid phase
Blend sample, continuous direct injected, afterwards using mass spectrum soft ionization method, obtain mixture in gas phase and liquid phase mass spectrograph
In each composition first mass spectrometric.Then under different disturbed conditions, each second order mses is obtained and are merged into two-dimentional mass spectrum,
And the two-dimentional mass spectrometry applications dynamics entropy minimum method (Kinetic EM) is studied, find independent ion therein and phase
Corresponding dynamic process.Then, using high-resolution mass-to-charge ratio (m/z) data of independent particle, each second order mses are extrapolated
The chemical formula of middle independent ion；Or compared with existing independent ion and Chemical kintics database, determine in each second order mses
The structural formula of independent ion；And then determine the chemical formula or chemical constitution of each composition in mixture.
Foregoing dynamics entropy minimum method (Kinetic EM) is to be based on entropy min algorithm (Entropy
MinimizationAlgorithm) develop.And entropy min algorithm (Entropy MinimizationAlgorithm)
It is to develop (to refer to C.E.Shannon, The Bell System based on Shannon entropy (Shannon Entropy)
Technical Journal,27(1948)379-423).Shannon entropy is applied to chemical analysis by Marc Garland etc. first
(referring to AnalyticaChimicaActa, 359 (1998) 303-310), and lock peak entropy minimum method is proposed based on this
(BTEM, Band-Target Entropy Minimization, refering to Organometallics, 21 (2002) 1982-
1990).This lock peak entropy minimum method is mainly used in analyzing infrared mixed spectrum.In order to by entropy min algorithm be applied to interpretation of mass spectra with
And automatically analyze removal overlap spectrum, Zhang Huajun also successively propose tBTEM methods (refer to J Am Soc Mass Spectrum,
14 (2003) 1295-1305), it is rebuild entropy minimum method (MREM, Multi-Reconstruction Entropy more
Minimization, refering to Applied Spectroscopy, 61 (2007) 1366-1372).This more reconstruction entropy minimum method can
Applied to interpretation of mass spectra, to replace global optimization method with local optimization methods, and search for pure spectrum automatically.
For the structure of non-principal component in quick and easy detection mixture, Zhang Huajun proposes a kind of entropy minimum that combines and calculated
Method calculates each independent ion and corresponding dynamic process in mass spectrograph, so as to analyze the method for unknown material structure, i.e.,
Dynamics entropy minimum method (Kinetic EM, refering to CN105842330A).The dynamics entropy minimum method is chosen mass spectrometric
One or more parameters set one group of difference numerical value under the disturbed conditions as disturbed conditions, in the disturbed conditions
Different value conditions under material to be detected is detected using mass spectrograph, obtain one group of mass spectrometric data (two-dimentional mass spectrum), lead to
Cross and apply entropy min algorithm, while calculate the various independent ions of two-dimentional mass spectrogram and their dynamic process, then carry out matter
Spectrum parsing, so as to be inferred to the structural formula of material to be detected.This method avoid conventional tandem mass spectrum technical Analysis it is unknown into
Point key problem, can be from the mutually relevant of complexity that is, the problem of interfered with each other between different secondary mass ions information
Among the secondary ion disturbed, very clearly accurately give each level of user mass spectrographic patch information so that user is not for
The shattering process of principal component is very clear, and then very fast and accurately qualitative non-principal component.
The dynamics entropy minimum method utilizes algorithm, in the case where being not required to artificial instruct, automatically finds only in shattering process
Vertical ion and corresponding dynamic process, and then cause the structure of the unknown material in quick analysis of mixtures to become possibility.The party
Method can rapidly and accurately in dynamic process difference, to mixture carry out qualitative analysis, no matter its composition is unknown
Or known, isomer and homologue for being difficult to differentiate between especially for mass-spectrometric technique etc., be a kind of easy point
The method for analysing unknown material structure.
A kind of rapid analysis method of chemical constitution of the application is further on the basis of dynamics entropy minimum method
Developing, it can quick and precisely, automatically analyze and identify the unknown material structure in mixture based on considerably less sample size,
The structure of each unknown material in gas phase mixture is especially quickly analyzed, so as to also overcome this area for a long time always
Thirst for the problem solved.Further, a kind of rapid analysis method for chemical constitution that the embodiment of the present application provides specifically includes
Following steps：
(1) by gas phase or liquid phase mixture sample introduction in gas phase or liquid phase mass spectrograph；
(2) the one of the mixture is obtained by analyzing the mixture in a manner of soft ionization by the mass spectrograph
Level mass spectrogram；
(3) in multiple quasi-molecular ions that the first mass spectrometric figure obtained from step (2) includes, a unknown or known molecular is chosen
First mass spectrometric peak, and choose one or more parameters when the mass spectrograph is detected as disturbed conditions, and set institute
One group of difference numerical value under disturbed conditions is stated, is further analyzed under the different value conditions of the disturbed conditions, is obtained
Multiple second order mses figures corresponding with the first mass spectrometric peak, the multiple second order mses that will be obtained afterwards under different disturbed conditions
Figure synthesis, obtains two-dimentional mass spectrometric data collection；
(4) the two-dimentional mass spectrometric data collection obtained to step (3) is calculated by dynamics entropy min algorithm, described in acquisition
Each independent ion at first mass spectrometric peak and corresponding dynamic process；
(5) each independent ion obtained for step (4), using the testing result of high-resolution mass spectrometer, extrapolate each
The chemical formula of individual independent ion, or, each independent ion and corresponding dynamic process that step (4) is obtained with it is known solely
The database of vertical ion and dynamic process compares, and determines the structural formula of each independent ion；
(6) chemical formula or structural formula of each independent ion obtained according to step (5), is inferred to the first mass spectrometric peak
Corresponding chemical formula or structural formula.
Further, a kind of typical implementation of the rapid analysis method for the chemical constitution that the embodiment of the present application provides can
Refering to Fig. 1.Further, abovementioned steps (1) include：Gas phase or liquid phase mixture are not done into any separation, and direct injected in
Gas phase or liquid phase mass spectrograph.
The application is used gas phase and liquid phase blend sample without any separation direct injected in gas phase and liquid phase mass spectrograph
Mode, without mixture is separated, sample requirement is considerably less.The method of non-principal component in existing analysis of mixtures,
It is generally necessary to more sample.Such as non-principal component is analyzed using NMR and usually requires purer component, it is therefore desirable to be substantial amounts of
Original stock carries out separating for several times purification, so as to obtain pure component, however, to can only obtain Gamma Magnitude sometimes other for this method
Sample, some non-principal components are even lost or corrupted during separating-purifying.Although using chromatographic technique need not pair
Mixture carries out excessive pre-treatment, but this technology only can be with the principal component in analysis of mixtures, but can not be to non-principal component
Carry out qualitative.The method that the application provides can be not required to carry out mixture by way of direct injected come analysis of mixtures
Separating-purifying obtains purer component, it is only necessary to several milligrams of sample, is not required to worry unknown or principal component is separating
It is lost and destroys in purification process, can also unknown in analysis of mixtures and principal component simultaneously.Therefore, compared to existing
Analysis method, the application provide method facilitate it is succinct, it is time saving and energy saving, be greatly reduced in analysis of mixtures it is unknown and it is known into
The time divided.
Further, foregoing direct injected mode also has another advantage.Generally under different disturbances, two dimension is obtained
Mass spectrum needs the more time (a few minutes), and in general gas chromatographic analysis mixture, the peak of each pure component, only occurs big
The general 6-8 seconds are less；So common GC-MS analysis methods, go to analyze with dynamics entropy minimum method, to some peak,
The time window of appearance is inadequate.But direct injection analysis method, because the composition in sample can be in longer time mistake
In journey (a few minutes to dozens of minutes), continuously by mass spectral analysis, so as to calm applied dynamics entropy minimum side
Method.
When unknown or principal component the chemical formula or structural formula in analysis of mixtures, the application uses soft ionization method
It is because soft ionization method can retain the molecule of the various composition in mixture rather than hard ionization method makes each composition powered
Structure.For example, ionize material using the method for chemi-ionization, then each material simply adds CH3 +, C2H5 +Deng so may be used
To retain original molecule structure while make its ionization, so as in first mass spectrometric (MS1) in retain original molecule information, so be beneficial to
Application method finally pieces together back the chemical formula or chemical constitution of initial molecule from each independent ion.Although the application equally may be used
Go to analyze the structure of ion therein applied to hard MALDI-MS, still, the ionization mode firmly such as electron bombardment (EI) can be by composition
It is broken, and simply obtain the MS based on quasi-molecular ions of each composition1.Therefore the independent ion of its generation can only be utilized to piece together back this
The structure of a little fragment ion peaks, can not obtain whole original molecule chemical formula or chemical constitution.Under EI ionization patterns, if EI
Voltage set very low, such as in below 10V, molecular ion peak can be obtained, in this case, can also
It is considered a kind of soft ionization mode.Retain original molecule structure in ionization, can be in MS1Many information is provided in mass spectra peak.
Such as can be from MS1A certain mass spectra peak in know unknown corresponding to this mass spectra peak or principal component molecular mass；Secondly,
The original molecule structure of reservation is broken under disturbance to obtain the chemical formula and structure of independent ion, can provide original molecule chemical formula and
The information of structure.Therefore, unknown or principal component generation independent ion information and molecular mass can be utilized to piece together back original
The chemical formula or chemical constitution of molecule.
When obtaining MS1Afterwards, because using soft ionization mode, a certain MS among these1Mass spectra peak i.e. represent it is a certain into
Point, the various composition in mixture can be along MS1M/z axles appear in from small to large in mass spectrogram.So due to each composition
Mass-to-charge ratio it is different, in mass spectrum, each composition has been separated in mixture, only need to select some ion every time, more
The secondary entropy of applied dynamics repeatedly minimum method, it from a sample, can just find the molecular formula or structure of multiple compositions therein
Formula.However, this MS1Mass spectra peak provide only the information of molecular mass, but can not directly provide the information on molecular structure.Institute
, as under disturbed conditions, the disturbance of different numerical value is set, further to smash a certain MS in one or more parameters1Mass spectra peak
The composition of representative.Same MS1Under different disturbed conditions, multiple second order mses figure (MS are can obtain2), by these MS2Spectrogram
Integrate, just obtain a two-dimentional mass spectrometric data.
Due to the ion that a certain material is formed in mass ions cracking process, its mass of ion and composition are all fixed
, its behavior is not disturbed by other components, only causes detected changes in amplitude by its change in concentration, and these ions are considered as
Independent ion.When to a certain MS1Unknown or the different numerical value of principal component setting the disturbance that mass spectra peak represents obtains multiple two levels
During mass spectrogram, this unknown or independent ion caused by principal component concentration can change, but other are characterized in fixing
, such as their m/z in mass spectrogram position, and the ratio of parent ion and isotope ion.Because its behavior is independent, i.e.,
The peak of each independent ion is overlapped, in two-dimentional mass spectrum, each independent ion can also be distinguished.Using Kinetic
EM, while each independent ion is told, it also can obtain the dynamic variation process of independent ion.
After obtaining each independent ion by parsing, using the result of high resolution mass spectrum, extrapolate each independence from
The chemical formula of son.Under normal circumstances, the mass-to-charge ratio error range of high resolution mass spectrum is within 5ppm, so can be according to very accurate
Mass-to-charge ratio value, the independent possible chemical formula of ion is calculated, or range shorter to several possible chemical formulas.Enter
One step, can also be last true with reference to other rules (" nitrogen rule " etc.) according to information such as the ratio between isotopic peak, positions
The chemical formula of the fixed independent ion.In this way, by high resolution mass spectrum, with reference to certain rule, you can extrapolate each independence from
The chemical formula of son.Because these rules can use mathematical notation, so just can automatically be judged using polyalgorithm each only
The chemical formula of vertical ion.
Even if without high-resolution mass spectrometer, after independent ion and corresponding dynamics data is obtained, can also by with
Existing independent ion and Chemical kintics database compare, to find the structural formula of each independent ion.By to known to different
Composition carries out Kinetic EM analyses, it is possible to obtains the independent ion and dynamics data of these principal components, and establishes base
In the independent ion and Chemical kintics database of principal component.Due to being to analyze principal component, the molecular formula of their independent ion
Or structural formula, and need not necessarily know, and need to only know the low resolution spectrogram and power of the independent ion of some composition
Process, and their data are stored in database.So when some unknown material or ion are applied in Algorithm
Kinetic EM, only it is to be understood that the spectrogram and dynamic process of its independent ion, it is possible to and existing independent ion and dynamic
Mechanical Data storehouse compares, and the structural formula corresponding to independent ion mass spectroscopy data is obtained, so as to obtain the knot of unknown material or ion
Structure formula.
Finally, according to the chemical formula or structural formula of obtained independent ion, and in MS1In obtain molecular ion point
Son amount, can be inferred that the MS1Unknown or principal component chemical formula or structural formula corresponding to mass spectra peak.
In present specification, the definition of foregoing " independent ion " is：Some component, group or broken in the mixture
Piece, its behavior pattern are not disturbed by other components, group or fragment.Its behavior pattern be to maintain it is consistent, change, only
It is due to that its change in concentration causes detected amplitude (such as abundance) to change, its feature (such as pure spectrum) does not change.
Further, abovementioned steps 1) in blend sample be directly entered mass spectrograph and analyzed without carrying out in advance
Separation, direct injected mode include being inserted directly into (direct insertion), are injected directly into (direct infusion) etc. and enter
Sample loading mode, and not limited to this.
Further, abovementioned steps 1) in mass spectrograph use can obtain two level above mass spectrometric data, and can be in difference
The mass spectrograph of various disturbances is provided in the mass spectrum shattering process of rank.Including quadrupole rod time of-flight mass spectrometer (Q-TOF-MS),
Triple level Four bar mass spectrographs (Triple Quadrupole MS), ion trap mass spectrometer (IT-MS), ion trap flight time mass spectrum
Instrument (IT-TOF), time-of-flight mass spectrometry instrument (Triple TOF MS), electrostatic field orbit trap combined type mass spectrum (LTQ-
Orbitrap MS) etc., and not limited to this.
Further, abovementioned steps 2) in soft ionization mode include chemi-ionization (CI), electro-spray ionization (ESI),
Atmospheric Pressure Chemical ionizes the common soft ionization method such as (APCI), substance assistant laser desorpted ionized (MALDI), and is not limited to
This.Further, abovementioned steps 3) described in disturbed conditions include electric-field intensity, magnetic field intensity, radiation intensity, vacuum, touch
Hit one or more of combinations in bulk of molecule and species, the wavelength of excitation source or intensity, and not limited to this.
Wherein, for MS2In some independent ion, if because molecular weight is too big, still can not use high resolution mass spectrum
Its qualitative chemical formula；Or the information of the not no independent ion of database, the MS to the independent ion can be used3Or MSnTwo
The application that mass spectrum carries out multiple Kinetic EM methods is tieed up, obtains the chemical formula or structural formula of the independent ion.
Wherein, the composition as much as possible in a certain mixture is analyzed if desired, it is only necessary to repeats abovementioned steps 3) extremely walk
It is rapid 6).A certain MS is chosen one by one1Mass spectra peak, increase one or more disturbances by changing a certain parameter and obtain two dimension
Mass spectrum, the information of independent ion is obtained by dynamics entropy minimum method, further extrapolates this MS1It is chemical corresponding to mass spectra peak
Formula or structural formula.By repeating abovementioned steps 3) to step 6), you can obtain the chemical formula or structure of multiple compositions in mixture
Formula.
Wherein, for the non-principal component in gas phase mixture, gas phase composition molecular weight is comparatively smaller, because
This, the mass-to-charge ratio of secondary mass spectrographic fragment ion is smaller.Because general molecule is all by C, H, O, N, S, Cl, F etc. common element
Composition, therefore, when each independent ion that certain gas phase composition is told by parsing, further obtained respectively by high resolution mass spectrum
After the chemical formula of individual independent ion, corresponding construction corresponding to its separate ionization formula is also easy to infer.It is only when obtaining these
After the structure of vertical ion, according to this composition in MS1The molecular weight information of offer, the molecular formula and structure of molecular ion are just very
Easily reduction.It so can be obtained by the information such as unknown in gas phase mixture or known component molecules structure.
The application provide only the basic idea of a kind of method of the chemical formula of material or structural formula in analysis of mixtures, bag
Contain but be not limited only to process described above.If for example, make mixture powered by the way of electron bombardment (EI), equally
Can be in MS1Obtain each fragment ion peak.When wondering MS1In molecular formula or structural formula representated by some fragment peak when,
This fragment peak can also be selected, in one or more parameters as disturbed conditions, and sets and is smashed under the disturbance of different numerical value, from
And obtain multiple MS2The two-dimentional mass spectrometric data of composition, then analyzed using dynamics entropy minimum method and obtain independent ion and
Dynamic process, then extrapolate by high resolution mass spectrum the chemical formula of each independent ion, or according to the independent ion of acquisition and dynamic
Mechanical Data storehouse and the comparison of existing independent ion and Chemical kintics database obtain the corresponding structural formula of each independent ion, most
Afterwards according to the chemical formula or structural formula of obtained independent ion, the MS is extrapolatednIn molecular formula representated by some fragment peak
Or structural formula.So the present processes can not only determine unknown in mixture and principal component chemical formula or chemistry knot
Structure, MS can also be determinednIn a certain fragment peak corresponding chemical formula or chemical constitution.
The drawings and examples of the application will be combined as follows, and further the technical scheme in the embodiment of the present application is carried out
Clearly and completely describe, it is clear that described embodiment is some embodiments of the present application, rather than whole embodiments.Base
Embodiment in the application, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belong to the scope of the application protection.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment 1：Gas phase composition structure based on gaseous mass analyzer is quickly analyzed
On the GC-CI-Q-TOF-MS instruments of an Agilent (Agilent), by separatory capillary in GC instruments
Chromatographic column separates GC, then connects only 3 meters of long short capillaries, and by one of the capillary without separative efficiency
2ml sealed sample bottle (fluid sample is housed) is connected, and keeps capillary to be higher than sample liquid level.The other end of capillary
Access in mass spectrograph.The sample bottle and capillary are placed in chromatographic capillary cavity.Setting GC heating schedule, such as from
2 DEG C of heating per minute, from 30 DEG C to 200 DEG C；And start mass spectral analysis.
Using GC heating schedule, slowly fluid sample is heated up, while using the negative pressure in mass spectrographic CI sources, will be gasified
Sample be directly sucked in mass spectrum.With the difference of temperature, the composition in the gas of suction is also different.Due in each time
Section, the component number in the gas of suction is reduced (compared to fluid sample), can so simplify MS1Mass spectrographic complexity, simultaneously
Also ion competition/suppression (Ion Competition/Ion Suppression) can be reduced, increases MS as far as possible1Abundance,
Beneficial to the MS of next stepnThe raising of the abundance of ion.Generally under different disturbances, obtaining two-dimentional mass spectrum needs the more time
(a few minutes), and in general gas chromatographic analysis mixture, the peak of each pure component, only probably there are the 6-8 seconds or less；
So common GC-MS analysis methods, go to analyze with Kinetic EM, to some peak, the time window of appearance is inadequate.
So slow heating schedule so that there is time enough to go to observe MS1Peak, and select some MS1Peak, disturbed in different
Under the conditions of dynamic, two-dimentional mass spectrum is obtained.
Select some MS1Peak, or the MS in one section of m/z section1Peak, by these peaks in different collision induced dissociations
Smashed under (Collision-Induced Dissociation, CID) energy, obtain different MS2Ion, and during with flight
Between (TOF) mass spectrum, obtain their high-precision mass-to-charge ratio data.
Using Kinetic EM, with regard to some MS can be obtained1The independent ion and dynamic process at peak, and the qualitative MS1Peak,
Also the composition in fluid sample can just be analyzed one by one, obtains their structural information.
Embodiment 2：Constituent structure based on liquid phase mass spectrograph is quickly analyzed
This experiment uses the silent winged LC-Quadrupole-Orbitrap-MS of match.Certain unknown material is dissolved in methanol solution, matched somebody with somebody
Into 10ug/mL solution, and it is put into and puts usually in the bottle of solvent, sample is utilized into a micro-injection pump (syringe pump)
ESI sources are slowly injected into, sample rate is 0.1mL/min.Mass Spectrometer Method pattern is ESI-.
Because sample is slowly expelled to ESI sources, therefore can obtain containing material MS1Mass spectrogram, this MS1Matter
In spectrogram, it can be deduced that this unknown material molecular ion m/z=440.For this MS1Different disturbed conditions are selected, obtain a system
Arrange MS2Peak, so as to be analyzed.On this instrument, different CID energy (0 arrives 180eV) is selected, is obtained a series of
MS2Data.By these MS2Aggregation of data get up, a graphics can be obtained, i.e., two-dimentional mass spectrometric data collection, as shown in Figure 2.
EM algorithms are applied on two-dimentional mass spectrometric data collection, independent ion A, B, C, D and E, and their change procedure can be obtained, such as
Shown in Fig. 3.
The broken of this unknown material, which is can be seen that, from dynamic variation process is divided into five steps.Shown in Fig. 4 A- Fig. 4 E
The process of dynamic variation can be better described in the mass spectrogram of each independent ion.
First, independent ion A includes molecular ion (molecular ion) m/z=440, and very low amount other from
Sub (m/z=311, m/z=422 etc.).When CID energy gradually rises, independent ion A concentration gradually rises, and reaches peak
Reduce again afterwards.Secondly, independent ion B is formed to the ion between m/z=430 by being heavily located at m/z=250, for example, m/z=
311, m/z=422, m/z=396 plasma.It is inferred that these ions are by the broken secondary ion formed of independent ion A.
Independent ion C is formed by being heavily located at the ion near m/z=175, and rule of thumb, these ions are that secondary ion continues to crush
The three-level ion of formation.The like, it can be deduced that independent ion D is level Four ion, and independent ion E is Pyatyi ion.
Next, by carefully analyzing high resolution mass spec, the ionic molecule that each mass spectrometric data represents can be inferred that
Formula.Due to being to take high resolution mass spectrum, the error range of mass-to-charge ratio is in 5ppm, it is possible to according to point-device mass-to-charge ratio,
The independent possible chemical formula of ion is calculated, or range shorter to several possible chemical formulas.
First, according to abundance highest quasi-molecular ions m/z=175.0495 in independent ion C, is obtained, there is this mass-to-charge ratio
Ion only has a kind of possibility of molecular formula, as C7H5N5O-, it is inferred that parent molecule at least contains 7 C atoms.
Afterwards, in independent ion B, it is m/z=311.0909, m/z=422.1230, m/z=to obtain the higher peak of abundance
396.1435, m/z=293.0803.These ions respectively obtain 3 kinds, 8 kinds, 8 kinds, 3 kinds of possible molecular formula.Wherein m/z
=311.0909 three kinds of possible molecular formula are respectively：C2H15N8O10 -,C16H13N3O4 -And C14H11N6O3 -, according to pushing away before
It is disconnected, 7 C atoms are at least contained in parent molecule, secondly, are restrained according to nitrogen, ion middle-molecular-weihydroxyethyl is odd number, then contains and even number nitrogen
Atom, it is concluded, therefore, that chemical formula is C14H11N6O3 -.And eight kinds of possibilities at m/z=422.1230 peak, exclude and be less than
14 C molecule, and the molecule less than 5 N, it is inferred to there was only C in 8 kinds of possibilities19H16N7O6 -Correctly.
Finally, the accurate mass m/z=440.1337 of the molecular ion in independent ion A is obtained, when setting mass-to-charge ratio is missed
Poor scope can obtain the possibility of six kinds of molecular formula within 5ppm, but according to deduction before, obtained C atomicities
Mesh, and the deduction restrained according to nitrogen, are inferred in six kinds of possibilities of molecular ion, only C19H18N7O6 -For molecular ion
Unique possibility.It can therefore be concluded that going out, original molecular formula is C19H19N7O6。
According to checking, this unknown material is really folate molecule, and its molecular formula is C19H19N7O6, and the deduction conclusion of the present embodiment
Unanimously.Therefore, according to the present processes, the molecular formula of unknown material can be successfully inferred to.
Embodiment 3：Constituent structure based on liquid phase mass spectrograph is quickly analyzed
On Taiwan Island Tianjin LC-IT-TOF instruments, by separatory liquid-phase chromatographic column short circuit (by pass) in LC instruments.
The solution for the 10ug/mL that methanol solution is made into is dissolved in using the folate molecule in a upper embodiment, and is put into and puts solvent usually
In bottle, it is not separated as mobile phase and is pumped directly into ESI sources, sample rate is 0.2mL/min.Mass Spectrometer Method pattern is ESI-.
According to the MS of folate molecule1Molecular ion m/z/=440 is obtained in spectrogram, on this instrument, the disturbance of selection
Condition is the disturbance of collision gas (collision gas) pressure：We by the setting of collision gas pressure from 0 to 100%, with
0.5% consecutive variations are spaced, change every time continues 500 milliseconds, finally obtains one and contains 200 MS2The two-dimentional mass spectrum of spectrogram
(Fig. 5).It is attached and, for this MS1Also other different disturbed conditions, such as magnetic field intensity, radiation intensity, colliding molecule may be selected
Size and species, the wavelength of excitation source or intensity etc., it is similar, can also obtain, obtain a series of MS2Peak, from
And analyzed.
This two-dimentional data set is analyzed using entropy min algorithm, obtained in different collision gas pressure inferior lobe acid dissociations
Independent ion A, B, C, and its dynamic variation process (Fig. 6).Independent ion A, B, C mass spectrogram can be obtained simultaneously
(Fig. 7).As can be seen here, under different collision gas pressure, folic acid is dissociated into different independent ions, and independent ion A is
Molecular ion, m/z=440, when impact pressure increases, molecular ion dissociation turns into independent ion B, and C, B include m/z=422
And two dissociating ions of m/z=311, C include m/z=396, m/z=378, m/z=293, m/z=175.Work as impact pressure
Continue to increase, independent ion B concentration reduces, and C concentration increases.When collision gas pressure is very high, because neutral lose, C
Concentration also begins to reduce.
It is high resolution mass spectrum because this embodiment uses IT-TOF, similar, we can also obtain each independent ion
High resolution mass spectrum.According to identical logic in embodiment 2, we can be final to obtain according to the high resolution mass spectrum of each independent ion
Chemical formula to parent-molecule ion is C19H18N7O6 -。
, also can be very accurate and then inventor is had found, other unknown materials are analyzed using foregoing each scheme
Its chemical formula of true judgement etc., and its accuracy has also arrived the checking of other characteristic manners known to industry.
Finally it should be noted that：Various embodiments above is only to illustrate the technical scheme of the application, rather than its limitations；To the greatest extent
The application is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from each embodiment technology of the application
The scope of scheme.
Claims (11)
- A kind of 1. rapid analysis method of chemical constitution, it is characterised in that including：(1) by gas phase or liquid phase mixture sample introduction in gas phase or liquid phase mass spectrograph；(2) the one-level matter of the mixture is obtained by analyzing the mixture in a manner of soft ionization by the mass spectrograph Spectrogram；(3) in multiple quasi-molecular ions that the first mass spectrometric figure obtained from step (2) includes, one unknown or known molecular one is chosen Level mass spectra peak, and one or more parameters when the mass spectrograph is detected are chosen as disturbed conditions, and disturbed described in setting One group of difference numerical value under the conditions of dynamic, is further analyzed under the different value conditions of the disturbed conditions, acquisition and institute The corresponding multiple two-dimentional mass spectrograms in first mass spectrometric peak are stated, it is afterwards that the multiple second order mses figures obtained under different disturbed conditions are comprehensive Close, obtain two-dimentional mass spectrometric data collection；(4) the two-dimentional mass spectrometric data collection obtained to step (3) is calculated by dynamics entropy min algorithm, obtains the one-level Each independent ion of mass spectra peak and corresponding dynamic process；(5) each independent ion obtained for step (4), using the testing result of high-resolution mass spectrometer, extrapolate each only The chemical formula of vertical ion, or, each independent ion and corresponding dynamic process that step (4) is obtained and known independence from The database of son and dynamic process compares, and determines the structural formula of each independent ion；(6) chemical formula or structural formula of each independent ion obtained according to step (5), it is corresponding to be inferred to the first mass spectrometric peak Chemical formula or structural formula.
- 2. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that step (1) includes：By gas phase Or liquid phase mixture does not do any separation, and direct injected is in gas phase or liquid phase mass spectrograph.
- 3. the rapid analysis method of chemical constitution according to claim 1 or 2, it is characterised in that：It is described in step (1) Gas phase or liquid phase mass spectrograph, which have, obtains more than two level mass spectrographic function, and can be carried in the mass spectrum shattering process of different stage For various disturbances.
- 4. the rapid analysis method of chemical constitution according to claim 3, it is characterised in that：In step (1), the gas phase Or liquid phase mass spectrograph includes quadrupole rod time of-flight mass spectrometer, triple level Four bar mass spectrographs, ion trap mass spectrometer, ion trap flight Any one in time mass spectrum instrument, time-of-flight mass spectrometry instrument or electrostatic field orbit trap combined type mass spectrograph.
- 5. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that：Soft electricity is used in step (2) Make that various unknown in gas phase or liquid phase mixture and principal component is powered from mode.
- 6. the rapid analysis method of chemical constitution according to claim 5, it is characterised in that：Soft ionization in step (2) Mode includes chemi-ionization method, electro-spray ionization method, Atmospheric Pressure Chemical ionization method, electron impact ionization method, Any one in substance assistant laser desorpted ionized method.
- 7. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that：What is used in step (3) disturbs Dynamic condition includes electric-field intensity, magnetic field intensity, radiation intensity, vacuum, the size of colliding molecule and species, the ripple of excitation source The combination of any one or more in long or intensity.
- 8. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that step (5) includes：Using each The high-resolution mass-to-charge ratio data of independent ion, reckoning obtain the chemical formula of each independent ion.
- 9. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that step (5) includes：By right Different known or non-principal component carries out the analysis of dynamics entropy minimum methods, obtains the independent ion of these compositions and corresponding Dynamic process, and establish the database of independent ion and dynamic process based on these compositions.
- 10. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that step (6) includes：Utilize The molecular information that the chemical formula of each independent ion that step (5) is obtained is obtained with step (3), be inferred to corresponding unknown material or The chemical formula of known substance.
- 11. the rapid analysis method of chemical constitution according to claim 1, it is characterised in that step (6) includes：Utilize The molecular information that the structural formula of each independent ion that step (5) is obtained is obtained with step (3), be inferred to corresponding unknown material or The structural formula of known substance.
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| CN110501413A (en) * | 2019-08-13 | 2019-11-26 | 中国科学院南京地理与湖泊研究所 | Based on the determination method of the dissolved organic matter molecular formula of FT-ICR MS |
| CN111122455A (en) * | 2019-12-20 | 2020-05-08 | 华南协同创新研究院 | Method for judging stability of food mycotoxin structure |
| CN112611798A (en) * | 2021-01-08 | 2021-04-06 | 中国计量科学研究院 | Online mass spectrum detection method for isomerides |
| CN113484400A (en) * | 2021-07-01 | 2021-10-08 | 上海交通大学 | Mass spectrogram molecular formula calculation method based on machine learning |
| CN114894949A (en) * | 2022-04-12 | 2022-08-12 | 北京清谱科技有限公司 | Lipid fine structure analysis process and control processing system |
| CN115439752A (en) * | 2022-09-22 | 2022-12-06 | 上海市环境科学研究院 | Method for identifying atmospheric organic species, computer device and storage medium |
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| CN111122455A (en) * | 2019-12-20 | 2020-05-08 | 华南协同创新研究院 | Method for judging stability of food mycotoxin structure |
| CN112611798A (en) * | 2021-01-08 | 2021-04-06 | 中国计量科学研究院 | Online mass spectrum detection method for isomerides |
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